Reaction products of dialkyl phosphorothiolothionates and mucohalic acids



United SW65 P t 9 REACTION PRODUCTS OF DIALKYL PHOSPHORO- THIOLOTHIONATES AND MUCOHALIC ACIDS No Drawing. Application September 24, 1956 Serial No. 611,760

7 Claims. 01. 260-461) This invention relates to new organophosphorus compounds and to a method of preparing said compounds. In a specific aspect, this invention relates to the reaction of dialkyl phosphorothiolothionates with mucohalic acids, and to the resulting reaction products.

Among the objects of this invention is to provide a novel synthesis of organophosphorus compounds, to provide new and useful organophosphorus compounds, to provide a method for producing new organophosphorus compounds from dialkyl phosphorothiolothionates, to provide novel products from the reaction of dialkyl phosphorothiolothionates and mucohalic acids, and to provide novel organophosphorus compounds useful in insecticide compositions. These and other objects will be apparent from the description and claims that follow.

wherein R has the same meaning asgiven above. It is to be noted that this equation is offered as a suggested mechanism of. reaction andis not to, be'construed as limiting the reaction to misrepresentation.- A preferred embodiment of the invention comprise'sthe products derived from dialkyl phosphorothiolothionate's' containing from 1 to 4 carbon atoms in each alkyl group, and mucochloric and mucobromic acids.

The compounds of this invention have been found to be extremely efifective insecticides. This valuable utilization is illustrated by the following.

Tests against mites and mite eggs were carried out in the following manner. Acetone solutions containing 5% of the candidate compounds were prepared and diluted with water to give, solutions containing 1000, 100, and 10 p. p. m. of the candidate compounds for testing. Two heavily infested bean leaves containing'both eggs and adult two-spotted mites (T. bimaculatus) were carefully dipped in the abovesolutions anddried in a gentle air stream. The leaves werethen placed on damp paper toweling in Petri dishes and observed after twenty-four hours for mortality among the adult mites. The leaves were observed again after seven days to determine the number of eggs killed by the treatment.

It should be noted that tests using acetone-water solutions (containing none of the toxicant) kill neither mites nor mite eggsg These are the blank runsreferred to in the. following table. I v

obncen- Kill Kill Toxicant tration, Mites, Mite p. p. m. Percent Eggs,

. Percent 1, mam: 0 0 o 2. Product of Example 1 1, 000 100 100 [(CZH50)2P(S)SH+HOOOCC1=CC1CHO] 19 V 3. Product of Example 2 1,000 100 v 100 [(OHaOhP (S) SH+HOOGCBr=OBrCHO1 198 r 2g gt;

no X-O-CHO where X is selected from the group consisting of bromine and chlorine, and R is a lower alkyl group containing from one to four carbon atoms.

The process of the invention can be advantageously carried out within a temperature range of 25 to 150 C. A preferred embodiment of this process can be effected by carrying out the reaction within the 25 to 125 C. range. If preferred, inert solvents can be used in the reaction, and such include the normally liquid hydrocarbons such as pentane, heptane, benzene, xylene, toluene and the like; other suitable solvents include the chlorinated hydrocarbons, ethers, esters, and similar solvents. However, in a preferred embodiment, the reaction is effected without the use of solvent media. Normally, advantageous results can be achieved with reaction periods varying from 1 to 8 hours. The following equation is oifered as generally illustrative of the mechanism of the process of our invention:

Similar tests were carried out utilizing other compounds of the invention derived from dialkyl phosphorothiolothionates and equally advantageous results were obtained.

In accordance with the above and in furtherance thereof, the following examples are olfered as illustrative of certain preferred embodiments of the invention.

Example 1.-Reacti0n product 0 muc ochloric acid and 0,0-diethyl phosphorozhiolorhionate Mucochloric acid (0.1 mole) and diethyl phosphorothiolothionate (0.1 mole) were mixed and heated carefully with stirring. At C., an exothermic reaction took place and HCl was evolved. The heating element was cut off; however, the hot Glas-Col heating mantle was left under the flask until the temperature of the reaction mixture had reached 125 C. Then the heating mantle was removed and the heat of reaction maintained the temperature at C. for several minutes. The reaction mixture was stirred for one hour and then placed under reduced pressure to remove any volatile impurities. The product is a yellow oil, 11 1.5379.

Example 2.Reacti0n product of m ucobro m ic acid anal- 0,0-dimethyl phosphorothiolothionate Example 3.Reaction product 07 mucobromic acid and 0,0-diisopr0pyl phosphorothiolothiamzte This product is a viscous orange oil and it was prepared from mucobromic acid (0.1 mole) and diisopropyl phosphorothiolothionate (0.1 mole) according to the-- procedure of Example 1.

Example 4.-Reactin product of mucochloric acid and '0,0-diisobutyl. phosphorothiotot hionote I This product is a viscousyellowoil and itwas'prep'ared from mucochlor ic acid (0.1 mole) and diislobutyl'phosphorothiolothionate (0.1 mole) accordingto the procedure of Example 1. i

Example 5.Reacti0 z prodzict of. mucobromic acid and 0.0-diethyl phosphorothiolothionate This compound was prepared from mucohromic acid (0.1 mole) and diethyl' phosphorothiolo'thionate (0.1' mole) according to the procedure of Example 1.

While the invention has been described in considerable detail with reference to certain preferred embodiments thereof variations and modifications can be efiected within the spirit 'and scope of the invention as described hereinabove and as defined in the appended claims.

We claim: 1. As new compositions of matter,

the compounds represented by the general formula:

ROS

v3. The.-organophosphorus compound of the formula:

CzH5O S I h-s-o-ooo11 CaHsO CIIIJCHO .4. The organophosphorus compound of the formula:

i -s-o-ooon 'onao Br-C-OHO 5. The organophosphorus compound of the formula:

oH 0 s H H g -S-(POOOH 7, E C- H9...- 1 (DH 1 f C CHz U 6. The organophosphorus co'rnpound of the formula:

:7. The organophosphorus compound of the formula:

2,578,652 Cassaday Dec. 18, 1951 

1. AS NEW COMPOSITIONS OF MATTER, THE COMPOUNDS REPRESENTED BY THE GENERAL FORMULA: 